Method For Synthesizing Silicoaluminophosphate-34 Molecular Sieves Using Monoisopropanolamine

Abstract

A method for synthesizing small crystals of silicoaluminophosphate-34 (SAPO-34) molecular sieves with high structural purity. The method includes first forming a slurry comprising monoisopropanolamine. Then, the slurry is aged to form an aged slurry. Finally, crystallization of silicoaluminophosphate molecular sieves comprising the SAPO-34 molecular sieves is induced from the aged slurry.

Claims

1. A method for synthesizing silicoaluminophosphate-34 (SAPO-34) molecular sieves, comprising: forming a slurry comprising monoisopropanolamine; aging the slurry to form an aged slurry; and inducing crystallization of silicoaluminophosphate molecular sieves comprising the SAPO-34 molecular sieves from the aged slurry.

2. The method of claim 1, wherein the slurry further comprises a source of phosphorus, a source of aluminium, and a source of silicon.

3. The method of claim 2, wherein the molar ratio of monoisopropanolamine to Al.sub.2O.sub.3 ranges from about 0.1 to about 3.

4. The method of claim 1, wherein the slurry further comprises one or more other structure directing agents.

5. The method of claim 4, wherein the other structure directing agents are selected from the group consisting of tetraethylammonium hydroxide, morpholine, diethylamine, and triethylamine.

6. The method of claim 4, wherein the other organic structure directing agents comprise tetraethylammonium hydroxide.

7. The method of claim 2, wherein forming the slurry comprises: combining the source of phosphorus and water to form a phosphoric solution; introducing the source of aluminium into the phosphoric solution; introducing the source of silicon into the phosphoric solution after the introduction of the source of aluminium; and introducing monoisopropanolamine into the phosphoric solution after the introduction of the source of silicon.

8. The method of claim 4, wherein forming the slurry comprises: combining the source of phosphorus and water to form a phosphoric solution; introducing the source of aluminium into the phosphoric solution; introducing the source of silicon into the phosphoric solution after the introduction of the source of aluminium; and introducing monoisopropanolamine and one or more other structure directing agents into the phosphoric solution after the introduction of the source of silicon.

9. The method of claim 1, wherein aging the slurry is performed by aging the slurry at a temperature within the range from about 10° C. to about 170° C. for a time within the range from about 0.5 to 72 hours.

10. The method of claim 1, wherein aging the slurry is performed by aging the slurry at a temperature within the range from about 20° C. to about 150° C. for a time within the range from about 1 hour to about 30 hours.

11. The method of claim 1, wherein the inducing crystallization step comprises: initially heating the aged slurry to a first temperature within the range from about 50° C. to about 170° C. and then holding the slurry at the first temperature for a time within the range from about 0.5 hour to about 24 hours; and further heating the aged slurry to a second temperature within the range from about 150° C. to about 250° C. and then holding the slurry at the second temperature for a time within the range from about 1 hour to about 100 hours.

12. The method of claim 1, wherein the inducing crystallization step comprises: initially heating the aged slurry to a first temperature within the range from about 80° C. to about 150° C. and then holding the mixture at the first temperature for a time within the range from about 1 hour to about 10 hours; and further heating the aged slurry to a second temperature within the range from about 170° C. to about 220° C. and then holding the slurry at the second temperature for a time within the range from about 5 hour to about 72 hours.

13. The method of claim 1, wherein the inducing crystallization step comprises: heating the aged slurry to a temperature within the range from about 150° C. to about 250° C. and then holding the slurry at the temperature for a time within the range from about 1 hour to about 100 hours.

14. The method of claim 1, wherein the inducing crystallization step comprises: heating the aged slurry to a temperature within the range from about 170° C. to about 220° C. and then holding the slurry at the temperature for a time within the range from about 5 hour to about 72 hours.

15. The method of claim 1, wherein the silicoaluminophosphate molecular sieves have a silicon ratio of about 0.01 to about 0.3.

16. The method of claim 1, wherein the silicoaluminophosphate molecular sieves have a silicon ration of about 0.03 to about 0.2.

17. The method of claim 1, wherein the average diameter of the SAPO-34 molecular sieves is smaller than 10 μm.

18. A catalyst particle for the conversion of methanol to olefins comprising the SAPO-34 molecular sieves of claim 1.

19. A catalyst particle for the conversion of methanol to olefins comprising the SAPO-34 molecular sieves of claim 16.

20. A process for producing olefins, the process comprising converting methanol to olefins in the presence of the catalyst particle of claim 19.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1 shows a method for synthesizing silicoaluminophosphate-34 (SAPO-34) molecular sieves in accordance with one embodiment of the present invention.

[0021] FIGS. 2A and 2B show a typical x-ray diffraction (XRD) pattern and a SEM image of the solid products obtained from Example 3 of the present application, respectively.

[0022] FIG. 3 shows an XRD pattern of the solid products obtained from Comparative Example 2 of the present application.

DETAILED DESCRIPTION

[0023] The present invention is described with reference to embodiments of the invention. Throughout the description of the invention, reference is made to FIGS. 1 to 3. When referring to the figures, like elements shown throughout are indicated with like reference numerals.

[0024] FIG. 1 shows a method for synthesizing silicoaluminophosphate-34 (SAPO-34) molecular sieves in accordance with one embodiment of the present invention. The method includes first forming a slurry comprising monoisopropanolamine. The slurry may include a source of phosphorus, a source of aluminium, and a source of silicon. Then, the slurry is aged to form an aged slurry. Finally, crystallization of SAPO molecular sieves comprising the SAPO-34 molecular sieves is induced from the aged slurry.

[0025] Non-limiting examples of suitable sources of phosphorous, which may also include aluminium-containing phosphorus compositions, include phosphoric acid, organic phosphates such as triethylphosphate, phosphate salts such as ammonium phosphate, tretraethylammonium phosphate, and crystalline or amorphous aluminophosphates such as AlPO.sub.4, phosphorus salts, or any combinations thereof. A preferred source of phosphorus is phosphoric acid.

[0026] Non-limiting examples of suitable sources of aluminium include organoaluminium compounds such as aluminium alkoxides and inorgarnic aluminium sources such as aluminium phosphate, aluminium hydroxide, sodium aluminate, boehmite, pseudo-boehmite, gibbsite and aluminium trichloride, or any combination thereof. A preferred source of aluminium is pseudo-boehmite.

[0027] Non-limiting examples of suitable sources of silicon include alkali silicate such as sodium silicate, fumed silica, organosilicon compounds such as tetraalkylorthosilicates, for example, tetramethylorthosilicate (TMOS) and tetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensions thereof, and silicic acid or any combination thereof. A preferred source of silicon is colloidal silica.

[0028] As shown in FIG. 1, the synthesizing method includes a forming step 100. At forming step 100, a slurry comprising monoisopropanolamine is formed. The slurry may include a source of phosphorus, a source of aluminium, and a source of silicon. The slurry may further include one or more other structure directing agents other than monoisopropanolamine. In one embodiment, the amounts of various components added into the slurry are determined according to the molar ratios shown in the following formula, i.e., aR.bSiO.sub.2.Al.sub.2O.sub.3.cP.sub.2O.sub.5.dH.sub.2O (Formula 1), wherein R is monoisopropanolamine alone or a mixture with other structure directing agents, a is the molar ratio of organic structure directing agent or agents to Al.sub.2O.sub.3 and varies in the range of 0.1-4.0, b is the molar ratio of SiO.sub.2 to Al.sub.2O.sub.3 and varies in the range of 0.02-2.0, c is the molar ratio of P.sub.2O.sub.5 to Al.sub.2O.sub.3 and varies in the range of 0.2-2.0, and d is the molar ratio of H.sub.2O to Al.sub.2O.sub.3 and varies in the range of 10 to 100. In the case that monoisopropanolamine is combined with other organic structure directing agent(s), the molar percentage of monoisopropanolamine over the total organic structure directing agents may range from 1% to 99%. In one embodiment, the molar ratio of monoisopropanolamine to Al.sub.2O.sub.3 may range from about 0.1 to about 3.0.

[0029] At forming step 100, the order of adding the starting components may vary, and the rates of adding the starting components may be 5 g or greater per minute. In one embodiment, the slurry is formed by first combining a source of phosphorus and water to form a phosphoric solution, to which a source of aluminium is introduced. Then, after the introduction of the source of aluminium, a source of silicon is introduced into the phosphoric solution. Finally, after the introduction of the source of silicon, monoisopropanolamine is introduced into the phosphoric solution to form a slurry. During and after the addition of the starting components, the slurry may be optionally mixed or agitated. The mixing of components may be performed at a temperature ranging from 10° C. to 100° C.

[0030] In another embodiment, the slurry is formed by first combining a source of phosphorus and water to form a phosphoric solution, to which a source of aluminium is introduced. Then, after the introduction of the source of aluminium, a source of silicon is introduced into the phosphoric solution. Finally, after the introduction of the source of silicon, monoisopropanolamine in conjunction with one or more other organic structure directing agent(s) is introduced into the phosphoric solution to form a slurry. Monoisopropanolamine and other organic structure directing agent(s) can be added to the aluminium, phosphorus and silicon containing slurry individually or in a form of a pre-mixed template mixture or mixture solution comprising monoisopropanolamine and other organic structure directing agents.

[0031] Non-limiting examples of suitable other structure directing agents include tetraalkyl ammonium compounds and amines including salts and substituted alkyl group connecting to nitrogen thereof, such as tetramethyl ammonium compounds, tetraethyl ammonium compounds, tetrapropyl ammonium compounds, and tetrabutylammonium compounds, cyclohexylamine, morpholine, propylamine, di-n-propylamine (DPA), tripropylamine, diethylamine (DEA), triethylamine (TEA), ethanolamine, N,N-diethanolamine, N,N-diethylethanolamine, diisopropanolamine, triisopropanolamine, N,N-dimethyl ethanolamine, N-methylethanolamine, N-methyldiethanolamine, triethanolamine, methanolamine, dimethanolamine, trimethanolamine, piperidine, cyclohexylamine, 2-methylpyridine, N,N-dimethylbenzylamine, dicyclohexylamine, choline, N,N′-dimethylpiperazine, N′,N′,N,N-tetramethyl-(1,6)hexanediamine, N-methyl piperidine, 3-methyl-piperidine, N-methyl cyclohexylamine, 3-methylpyridine, 4-methyl-pyridine, quinuclidine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, diisopropylamine, t-butyl-amine, ethylenediamine, pyrrolidine, 2-imidazolidone and diglycolamine. Preferred other structure directing agents are tetraethylammonium hydroxide, morpholine, diethylamine and triethylamine.

[0032] After forming step 100 is completed, the method continues to aging step 102.

[0033] At aging step 102, the slurry is aged. The slurry may be aged at a temperature ranging from about 10° C. to about 170° C., preferably from about 20° C. to about 150° C., for any period of time longer than 0.5 hours, preferably from about 0.5 hour to about 72 hours, and more preferably from 1 hour to 30 hours. Other methods of aging or assisting in the aging of the slurry include mechanical agitation, and/or milling, and/or sonication.

[0034] Without being held to a particular theory, it is believed that at forming step 100 and aging step 102, silicon, aluminium, and phosphorus sources disassociate from their respective original forms, and these dissociated species are rearranged to form Al—O—P—O and/or Si—O—Al—O—P—O linkages. No SAPO-34 crystalline phase is detected under X-Ray Diffraction at these steps.

[0035] After aging step 102 is completed, the method continues to inducing crystallization step 114.

[0036] At inducing crystallization step 114, crystallization of SAPO molecular sieves comprising the SAPO-34 molecular sieves is induced from the aged slurry. In one embodiment of the invention, crystallization is induced by a heating protocol using two steps, i.e., a first heating step 104 and a second heating or crystallization step 106.

[0037] At first heating step 104, the slurry is additionally aged under a high temperature to ensure the formation and mixing of the crystal nuclei precursors, nuclei and/or crystallites throughout the entire slurry. In one embodiment, the aged slurry is initially heated to a first temperature ranging from about 50° C. to about 170° C., preferably from about 80° C. to about 150° C., and then held at the first temperature for a time ranging from about 0.5 hour to about 24 hours, preferably from about 1 hour to about 10 hours. It is believed that this further maturation via first heating step 104 induces the formation of uniform crystals. After first heating step 104 is completed, the method continues to crystallization step 106.

[0038] At crystallization step 106, the slurry is further heated to a second temperature and held at the second temperature for a certain amount of time. In one embodiment, the slurry is further heated to a second temperature ranging from about 150° C. to about 250° C., preferably from about 170° C. to about 220° C., and then held at the second temperature for a time ranging from about 1 hour to about 100 hours, and preferably from about 5 hour to about 72 hours. In general, this second temperature should be higher than the first temperature at first heating step 104.

[0039] Without being held to a particular theory, it is believed that at crystallization step 106, amorphous phase and/or other precursory phase(s) transfer into SAPO-34 structure, and crystals grow to certain size. In one embodiment, the average diameter of SAPO-34 crystals is smaller than 10 μm, and the silicon ratio of SAPO-34 crystals is within the range from about 0.01 to about 0.3, and preferably from about 0.03 to about 0.2.

[0040] Another embodiment of inducing crystallization step 114 may include a single heating step protocol, in which the aged slurry is heated to a temperature that is the same as the second temperature at crystallization step 106, but at a heating rate not faster than 20° C. per minute. In one embodiment, the aged slurry is heated to a temperature within the range from about 150° C. to about 250° C., preferably from about 170° C. to about 220° C., and then holding the slurry at the temperature for a time within the range from about 1 hour to about 100 hours, preferably from about 5 hours to 72 hours. After inducing crystallization step 120 is completed, the method continues to separating step 108.

[0041] At separating step 108, SAPO molecular sieves comprising the SAPO-34 molecular sieves are recovered from the product slurry. Separating step 108 may include separation of the SAPO solids from the product slurry and washing of the SAPO solids. Non-limiting examples of separation equipments include vacuum filtration using filter cloth or paper, filter belts, filter presses, centrifuges, and/or membrane filters. Separating step 108 may be performed at a temperature ranging from 10 to 100° C., and preferably from room temperature to 70° C. In one embodiment, the solid SAPO molecular sieves may be separated by a filtration step through filters such as belt filters, filter presses, and membrane filters, and/or through centrifuges. The separated solid SAPO molecular sieves are then washed by water. The washing may be performed using separation equipment described above with the temperature of the washing water ranging from 10 to 100° C., and preferably from room temperature to 70° C. The purpose of the washing is to remove the residual compounds/salts from the recovered SAPO solids. The number of washing steps and the amount and pH of washing water are adjusted to ensure that the recovered SAPO solids are devoid of any impurities. For example, if sodium silicate is used as a silicon precursor, it may be advantageous to acidify the washing water or ammonium salt solution such as ammonium sulfate, chloride and phosphate to remove the residual sodium impurity from the recovered SAPO solids. After separating step 108, the solid SAPO molecular sieves are collected. The water content in the solid SAPO molecular sieves may be less than 80% by weight, and preferably less than 60% by weight. After separating step 108 is completed, the method continues to drying step 110.

[0042] At drying step 110, the SAPO molecular sieves comprising the SAPO-34 molecular sieves are dried to become free flowing powders. In one embodiment, the SAPO molecular sieves comprising the SAPO-34 molecular sieves are dried in a static oven, flash dryer, and/or tumbling dryer at a temperature ranging from 50° C. to 250° C., and preferably from 80° C. to 150° C. under the atmospheric condition or a flow of gas such as air. The water content in the SAPO molecular sieves after drying step 110 may be less than 20%, and preferably less than 10%.

[0043] After drying step 110 is completed, the SAPO-34 molecular sieves may have a chemical composition described on an anhydrous basis as mR:(Si.sub.x.Al.sub.yP.sub.z)O.sub.2 wherein m is in the range of 0.02 to 0.2, x in the range of 0.01 to 0.3, y in the range of 0.3 to 0.6, and z in the range of 0.3 to 0.6. After drying step 110 is completed, the method continues to calcining step 112.

[0044] At calcining step 112, the SAPO molecular sieves comprising the SAPO-34 molecular sieves are calcined to remove or burn off the residual organic structure directing agent or agents. The SAPO molecular sieves comprising the SAPO-34 molecular sieves may be calcined in a static furnace, moving bed furnace and/or rotary calciner at a temperature ranging from 350° C. to 950° C. under the atmospheric condition or a flow of gas such as air, oxygen, or nitrogen. Air is preferred. The calcination conditions are adjusted in a manner such that the total carbon left behind from the residual organic structure directing agent or agents in the calcined solid product may be not more than 5%, and preferably not more than 1%. The total weight loss of the calcined solid product may be not more than 15%, and preferably not more than 10% at 850° C. for 5 hours.

[0045] The SAPO molecular sieves comprising the SAPO-34 molecular sieves from separating step 108, drying step 110 and/or calcining step 112 may be further combined with formulating agents such as a matrix material and a binding agent to form catalyst particles. In one embodiment, the SAPO molecular sieves used to make catalyst particles comprise one or more metal elements from groups 1 to 14 such as transition metal elements. The metal elements may be incorporated by introducing metal containing compounds such as metal salts or/and hydroxides to the slurry during forming step 100 or aging step 102. In another embodiment, metal containing compounds may be introduced into SAPO molecular sieves after crystallization step 106 through physical mixing, ion-exchange, and/or impregnation.

[0046] The particle size of these catalyst particles may be in a range from 10 microns to 5 millimeters depending on the type of reactor operation. For example, for a fluidized bed reactor, an average particle size from 10-150 microns, preferably from 50-100 microns, is suitable. For a fixed bed operation, an average particle size from 1 mm-5 mm, preferably from 1.5-3 mm, is suitable.

[0047] The weight percentage of the SAPO molecular sieves comprising the SAPO-34 molecular sieves on a dry basis in the catalyst particles may be from 20 to 90%. The matrix material is preferably selected from clays such as kaolin, with a weight percentage ranging from 20 to 90% in the catalyst particles. The matrix material may be one or a combination of two or more materials. The matrix material typically plays the role of a filler to reduce cost and/or control diffusion of reactants and products throughout the catalyst particles.

[0048] The binding agents may comprise aluminium based or silicon based binders. Non-limiting examples of binding agents include aluminium nitrate, aluminium chloride, aluminium chlorohydrol, aluminium sulphate, aluminium phosphate, peptized alumina, peptized aluminium hydroxide, alumina sol, silica sol, and any combination thereof, with a weight percentage ranging from 5% to 30% in the catalyst particles. The binding agent is used to bind catalytically active component such as SAPO-34 in this invention with the matrix material such as clays to form shaped particles with desirable strength.

[0049] The SAPO molecular sieves comprising the SAPO-34 molecular sieves and the formulating agents may be mixed with or without mechanical grinding, and the mixture is then converted into particles of desirable size and shape, followed by a calcination step at a temperature ranging from 200° C. to 950° C. for a time ranging from 1 hour to 10 hours under the atmospheric condition or a flow of gas such as air. In one embodiment, the mixture is spray dried to form spherical particles with an average size ranging from 10 to 200 μm, and preferably from 50 to 100 μm.

[0050] The formulated catalyst may be used in the conversion of light oxygenates to light olefins. The light oxygenate feedstocks include alcohols, aldehydes, ketones, ethers, or mixtures thereof, and more preferably light alcohols and ethers containing 1-6 carbon atoms. It is particularly advantageous to use SAPO-34 of high structural purity, as disclosed herein, for the conversion of methanol to olefins (MTO) as described by Kaiser (U.S. Pat. No. 4,499,327).

[0051] Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to the following examples.

EXPERIMENTS

[0052] Structure is measured by X-Ray Diffractometer (PRO MPD from PANalytical) with voltage of 45 kV and current of 40 mA, using Cu-target at λ=1.54 Å. The samples for all XRD measurement are prepared by drying 5 grams of solid products obtained from separating step 108 during the synthesis at 120° C. for 5 hours. The dried solid products are further crushed into powders if necessary for XRD measurement. Crystal size is measured under SEM, where two areas of samples are randomly selected and imaged under various magnifications. The average of diameters of forty SAPO-34 crystals, twenty in each selected area, is taken. Molar ratio of Si/(Si+Al+P) is calculated from SiO.sub.2%, Al.sub.2O.sub.3% and P.sub.2O.sub.5% by weight which are analyzed by Inductively Coupled Plasma method.

Example 1

[0053] 5.2 g of 85% phosphoric acid (H.sub.3PO.sub.4).sub.and 15.7 g of H.sub.2O were combined to form a diluted H.sub.3PO.sub.4 solution. Then, 3.0 g of Catapal® B alumina was added under agitation to the diluted H.sub.3PO.sub.4 solution to form a homogeneous mixture. After the addition of Catapal® B was completed, 2.7 g of Ludox® AS-30 colloidal silica (30 wt. % of SiO.sub.2) was added into the mixture under agitation until the mixture became homogeneous. Finally, after the addition of Ludox® AS-30 was completed, 3.4 g of monoisopropanolamine (MiPA) was added under agitation to form a slurry. The slurry was further stirred at room temperature for about 24 hours to obtain an aged slurry. The composition of the initial gel was as follows: [0054] 2.0MiPA:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:50H.sub.2O

[0055] The gel was transferred into a Teflon-lined stainless steel autoclave, and heated to a temperature of 120° C. and held at the temperature of 120° C. for 5 hours, and then was further heated to a temperature of 200° C. and held at the temperature of 200° C. for 60 hours under autogenous pressure. The obtained solid product was centrifuged, washed, dried and calcined. The major XRD peaks of the dried product are shown in Table 1, indicating a SAPO-34 structure. The final product on anhydrous basis showed the following composition: Si.sub.0.15Al.sub.0.48P.sub.0.37O.sub.2.

TABLE-US-00001 TABLE 1 2θ, degree d-spacing, Å Relative Intensity, % 9.49 9.32 100 12.87 6.88 25.41 16.01 5.54 34.98 17.75 5.00 18.34 20.59 4.31 99.79 21.98 4.04 10.73 23.04 3.86 14.36 24.90 3.58 47.11 25.90 3.44 17.35 30.58 2.92 39.74 31.03 2.88 21.36 34.46 2.60 6.8 35.96 2.50 5.4

Example 2

[0056] The synthesis was conducted in the same fashion as Example 1 except using less Ludox As-30 to make the initial gel. The composition of the initial gel was shown as follows: [0057] 2.0MiPA:0.2SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:50H.sub.2O

[0058] After crystallization, the resultant product showed the same XRD characteristic peaks as those in Table 1. The final product on anhydrous basis showed the following composition: Si.sub.0.01Al.sub.0.48P.sub.0.48O.sub.2.

Example 3

[0059] 118.1 g of 85% phosphoric acid (H.sub.3PO.sub.4) and 238.7 g of H.sub.2O were combined to form a diluted H.sub.3PO.sub.3 solution. Then, 68.2 g of Catapal® B alumina was added under agitation to the diluted H.sub.3PO.sub.4 solution to form a homogeneous mixture. After the addition of Catapal® B was completed, 61.9 g of Ludox® AS-30 colloidal silica (30 wt. % of SiO.sub.2) was added into the mixture under agitation until the mixture became homogeneous. Finally, after the addition of Ludox® AS-30 was completed, a premixed solution containing 69.7.1 g of MiPA and 43.4 g of 35%0 of tetraethylammonium hydroxide (TEAOH) was added under agitation to form a slurry. The slurry was further stirred at room temperature for about 24 hours to obtain an aged slurry. The molar ratio of the initial gel was as follows: [0060] 1.8MiPA:0.2TEAOH:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:40H.sub.2O

[0061] The above aged slurry was transferred to a 1 L autoclave with an agitation rate of at least 100 rpm. The mixture of aged slurries was initially heated to a temperature of 150° C. and held at the temperature of 150° C. for 2 hours under autogenous pressure. Then, the mixture of aged slurries was further heated to a temperature of 190° C. and held at the temperature of 190° C. for 16 hours under autogenous pressure. The obtained solid product was filtered, washed, dried, and calcined. FIGS. 2A and 2B show a typical x-ray diffraction (XRD) pattern and a SEM image of the solid products obtained, respectively. The major XRD peaks of the dried product are shown in Table 2, indicating a SAPO-34 structure. The composition of the final product on anhydrous basis was as follows: Si.sub.0.18Al.sub.0.46P.sub.0.35O.sub.2.

TABLE-US-00002 TABLE 2 2θ, degree d-spacing, Å Relative Intensity, % 9.58 9.23 92.48 12.91 6.86 20.86 14.16 6.25 12.27 16.07 5.51 46.5 18.08 4.91 20.87 20.64 4.30 100 23.13 3.84 6.42 24.92 3.57 6.59 25.30 3.52 19.9 25.91 3.44 17.1 30.61 2.92 34.5 31.34 2.85 14.9 34.46 2.60 6.46

Example 4

[0062] The synthesis was conducted in the same fashion as Example 3 except that initial gel composition was different. The composition of the initial gel was shown as follows: [0063] 1.6MiPA:0.4TEAOH:0.2SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:40H.sub.2O

[0064] After crystallization, the resultant product showed the same XRD characteristic peaks as those in Table 2. The final product on anhydrous basis showed the following composition: Si.sub.0.08Al.sub.0.50P.sub.0.42O.sub.2

Example 5

[0065] 5.8 g of 85% phosphoric acid (H.sub.3PO.sub.4) and 10.3 g of H.sub.2O were combined to form a diluted H.sub.3PO.sub.4 solution. Then, 3.3 g of Catapal® B alumina was added under agitation to the diluted H.sub.3PO.sub.4 solution to form a homogeneous mixture. After the addition of Catapal® B was completed, 1.0 g of Ludox® AS-30 colloidal silica (30 wt, % of SiO.sub.2) was added into the mixture under agitation until the mixture became homogeneous. Finally, after the addition of Ludox® AS-30 was completed, a mixture of 1.1 g of MiPA, 2.1 g of diethanolamine (DEtA) and 6.3 g of 35% TEAOH solution was added under agitation to form a slurry. The slurry was further stirred at room temperature for about 24 hours to obtain an aged slurry. The molar ratio of the initial gel was as follows: [0066] 0.6MiPA:0.8DEtA:0.6TEAOH:0.2SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:40H.sub.2O

[0067] The gel was transferred into a Teflon-lined stainless steel autoclave, and heated to a temperature of 120° C. and held at the temperature of 120° C. for 5 hours, and then was further heated to a temperature of 200° C. and held at the temperature of 200° C. for 60 hours under autogenous pressure. The obtained solid product was centrifuged, washed, dried and calcined. After crystallization, the resultant product showed the same XRD characteristic peaks as those in Table 2.

Example 6

[0068] 118.9 g of 85% phosphoric acid (H.sub.3PO.sub.4) and 268.6 g of H.sub.2O were combined to form a diluted H.sub.3PO.sub.4 solution. Then, 68.6 g of Catapal® B alumina was added under agitation to the diluted H.sub.3PO.sub.4 solution to form a homogeneous mixture. After the addition of Catapal® B was completed, 62.3 g of Ludox® AS-30 colloidal silica (30 wt. % of SiO.sub.2) was added into the mixture under agitation until the mixture became homogeneous. Finally, after the addition of Ludox® AS-30 was completed, a mixture of 54.5 g of MiPA and 27.1 g of morpholine was added under agitation to form a slurry. The slurry was further stirred at room temperature for about 24 hours to obtain an aged slurry. The molar ratio of the initial gel was as follows: [0069] 1.4MiPA:0.6morpholine:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:40H.sub.2O

[0070] The gel was transferred into a Teflon-lined stainless steel autoclave, and heated to a temperature of 150° C. and held at the temperature of 150° C. for 2 hours, and then was further heated to a temperature of 190° C. and held at the temperature of 190° C. for 16 hours under autogenous pressure. The obtained solid product was centrifuged, washed, dried and calcined. The dried product showed a SAPO-34 structure from the XRD measurement. The composition of the final product on anhydrous basis was as follows: Si.sub.0.18Al.sub.0.47P.sub.0.35O.sub.2.

Example 7

[0071] 58 g of 85% phosphoric acid (H.sub.3PO.sub.4) and 9.9 g of H.sub.2O were combined to form a diluted H.sub.3PO.sub.4 solution. Then, 3.3 g of Catapal® B alumina was added under agitation to the diluted H.sub.3PO.sub.4 solution to form a homogeneous mixture. After the addition of Catapal® B was completed, 1.0 g of Ludox® AS-30 colloidal silica (30 wt. % of SiO.sub.2) was added into the mixture under agitation until the mixture became homogeneous. After the addition of Ludox® AS-30 was completed, a premixed solution containing 3.0 g of MiPA and 6.3 g of TEAOH solution was added under agitation to form a slurry. Finally, 0.6 g of 40% of HPF.sub.6 solution was added to the above slurry. The slurry was further stirred at room temperature for about 24 hours to obtain an aged slurry. The molar ratio of the initial gel was as follows: [0072] 1.6MiPA:0.6TEAOH:0.2SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:0.07HPF.sub.6:40H.sub.2O

[0073] The gel was transferred into a Teflon-lined stainless steel autoclave, and heated to a temperature of 120° C. and held at the temperature of 120° C. for 5 hours, and then was further heated to a temperature of 200° C. and held at the temperature of 200° C. for 30 hours under autogenous pressure. The obtained solid product was centrifuged, washed, dried and calcined. The calcined product showed a SAPO-34 structure from the XRD) measurement. The composition of the calcined product on anhydrous basis was as follows: Si.sub.0.06Al.sub.0.51P.sub.0.43O.sub.2.

Comparative Example 1

[0074] The synthesis was conducted in the same fashion as Example 1 except using diethanolamine (DEtA) instead of isopropanolamine (MiPA) as template to make the initial gel. The composition of the initial gel was shown as follows: [0075] 2.0DEtA:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:50H.sub.2O

[0076] After crystallization, the resultant product showed major XRD peaks at two theta 7.52°, 19.82°, 21.03° and 22.46°, indicating the product was mainly SAPO-5.

Comparative Example 2

[0077] The synthesis was conducted in the same fashion as Example 1 except using diisopropanolamine (DiPA) instead of isopropanolamine (MiPA) as template to make the initial gel. The composition of the initial gel was shown as follows: [0078] 2.0DiPA:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:50H.sub.2O

[0079] After crystallization, the resultant product showed a mixture of SAPO-34, SAPO-5 and unidentified impurity phase(s) with main XRD peaks at 2θ=8.16° and 21.13°. FIG. 3 shows an XRD pattern of the solid products obtained.

Comparative Example 3

[0080] The synthesis was conducted in the same fashion as Example 3 except using diethanolamine (DEtA) instead of isopropanolamine (MiPA) as template to make the initial gel. The composition of the initial gel was shown as follows: [0081] 1.6DEtA:0.4TEAOH:0.6SiO.sub.2:1.0Al.sub.2O.sub.3:1.0P.sub.2O.sub.5:40H.sub.2O

[0082] After crystallization, the resultant product showed a mixture of SAPO-34 and SAPO-5 from the XRD measurement.